3, 3, 3-trichloro-2-alkyl-2-nitropropanols and method for preparation thereof



. res 3?" atenro "ice Patented Apr. 5,196.0

1 2" W tion mixture is maintained at the latter temperature from 2 93 339 about l2 hours to 20 hours. Thereafter, the unreacted .s,s,3.rnrcHLono-2-Arro1t-z-mrnornorxNots AND ME moo non PREPARATION THEREOF Donald G. Kundiger and Gene F. Morris, Manhattan,

Kans., assignors to The'Dow Chemical Company, Mid- 7 land, Mich., a corporation of Delaware No Drawing. Application October 6, 1958 Serial No. 765,293

4 Claims. (Cl. 260-633) The present invention is concerned with 3,3,3-trichloro- Z alkyl-Z-nitropropanols represented by the formula 'cno-e-cnzon In this and succeeding formulae, R represents a lower alkyl radical containing from 1 to 4 carbon atomsfinelusive. More specifically the invention is concernedwith -new methods for preparing 3,3,3-trichloro-2-alkyl-2-nitropropanols and embraces new compounds prepared in accordance with this invention, particularly 3,3,3-tr ichloro- 2-methyl-2-nitropropanol.

Trichloronitro-propanols are useful as parasiticides such as for the control of nematodes, bacteria andfungi. They are also useful as herbicides, particularly for the control of aquatic plants.

Trichloronitropropanols are crystalline white solids, soluble in organic solvents such as alcohol chlorinated hydrocarbons and aliphatic nitro alcohols; dilute aqueous .sodium hydroxide, sodium bicarbonate and hydrochloric acid solution; and substantially insoluble in water.

According to this invention, 3,3,3-trichloro-2-alkyl- Z-nitropropanols may be prepared by the reaction of 3,3-dichloro-2-alkylallyl alcohol having the structure with a nitrogen oxide oxidizing agent. By nitrogen oxide oxidizing agent is meant dinitrogen tetroxide (N 0,) or concentrated nitric acid.

' The reaction appears to take place by a'- free radical mechanism with the third chlorine atom of the product "originating from another molecule of the reactant. The by-products in the reaction include material resulting from the dechlorination of the reactant 3,3-dichloro-2- 'alkylallyl alcohol. 1

The preferred method for the preparation of the 3,3,3- trichloro2-alkyl-Z-nitropropanols is by oxidizing the corresponding 3,3-dichloroe2-alkylallyl alcohol with dinitrogen tetroxide. molar proportion or a slight excess of the dinitrogen tetroxide is employed 'for'each molar proportion of the 3,3-dichloro-2-alkylallyl alcohol. The reaction is carried 'out in a suitable solvent such as carbon tetrachloride or ethylene dichloride. The reactiontakes place in the temperature range of from about -50 C. to 25- C. It is fprefer'red, however, that the initial reaction temperature be well below C. The time usually required to complete the reaction to obtain the desired 3,3,3-trichl0ro- Z-alkyl-Z-nitropropanol is from about 12 to 30 hours.

In carrying out the reaction, 3,3-dichloro-2-alkylallyl alcohol and dinitrogen tetroxide are mixed together in a suitable solvent at a temperature of about -S0 C. The mixture is maintained below 0 C. for a period of about 8 to 12 hours and thereafter allowed to warm to a temperature in the range of from 15 C. to 30 C. The reacthe reaction mixture.

55 Good results are obtained when an equiv {.dinitrogen tetroxide and solvent arerernoved by vaporization. and the desired 3,3,3-trichloro-2-alkyl-2-nitropro;-

.erate the vigor of the reaction. and, to subsequently increase the temperature toa maximum of about 30 C. The reaction is generally complete in from one to three hours after the reactants are mixed together.

In carrying out the reaction by the second procedure, the appropriate 3,S-dichloro-Z-alkylallyl alcohol is added portionwise to aqueous concentrated nitric acid maintained in the temperature range of from about 5 C. to about 10 C. A reaction takes place during the addition with the evolution of nitrogen oxide and nitrogen dioxide gases. After completion of the addition, the reaction mixture may be allowed. to warm gradually to about 25 to 30? C. Thereafter the nitrogen oxide gases still re- .main inginthe reaction mixture are removed by any one or a combination ofthe following procedures: (1) alternately cooling and warming between the temperatures of about 12 C. and 30 CI, (2) subjecting the reaction mixture to a reduced pressure of from 10 to 20 millimeters of mercury, or (3) bubbling nitrogen gas through After the removal of the nitrogen oxide gases is substantially complete, the reaction mixture is treated with. an alkali metal bicarbonate solution to render the reaction mixture substantially neutral. The organic portion is separated from the aqueous portion according to conventional procedures. The organic 'portion is then heated to distill out low-boiling by-products and to obtainthe desired 3,3,3-trichloro-2-methyl-2-nitropropanol product as a white solid residue. The latter is fractionally crystallized from a chlorinated hydrocarbon solvent to obtaina purified product. i The product may be further purified, if desired, by procedures known to those skilled in the art.

The following examples illustrate the invention but are not to be construed as limiting.

Example 1.3,3,3-trichloro-2mtethyl-Z-nitropropanol NO: .ClaC.&-C.H:OH

grams (0.7 mole) of 3,3-dichloro-2-methylallyl alcohol (precooled to -10". C.) was added to a solution of 70 grams (0.76 mole) of dinitrogen tetroxide in. 200 milliliters of chloroform, previously cooled .to +50? C. in a Dry Ice-chloroform bath. The reaction mixture was allowed to stand overnight in the cooling bath during which time the solution'warmed to --11 C. The mixture was then allowed to warm to room temperature and maintained at that temperature for 16 hours. Thereafter, excess dinitrogen tetroxide and chloroform solvent were removed byvaporization under normal-water-pump vacuum pressure and to obtain as a white solid residue 100 grams of a 3,3,3-trichloro-2-methyl-2-nitropropanol product. The latter onre'crystallization from carbon tet- .period of about 15 minutes.

raehloride had a melting point of l95 196 C- The product had elemental analyses as follows:

n NV (:1

Calculated 21.6 2.7 6.3 Found 22.2 2.8 6.2

Che--oni-O-t'i-CH;

CH: The acetate had elemental analyses as follows:

C H N Cl Calculated 40. 2 Found Example 2.--3,3,3-trichlor0-2-mthyl-Z-nitropropanol 141 grams (1.0 mole) of 3,3-dichloro-2-methylallyl alcohol was added portionwise to 130 milliliters (2.0

moles) of aqueous 70 percent nitric acid (specific gravity 1.42). The nitric acid solution was cooled to 3 C. prior to the addition and the reaction mixture maintained in the temperature range of between 3 to +2 C., during the addition of about 90 percent of the 3,3-dichloro-Z-methylallyl alcohol. An exothermic reaction took place during the addition with the evolution of nitrogen oxide and nitrogen dioxide gases. Thereafter the reaction mixture was allowed to warm to about'l4" C. over a period of 1 hour. There was continued evolution of the nitrogen oxide gases. The mixture was then cooled to 5 C. and the remaining alcohol added portionwise over a period of about 1 hour while the temperature was maintained between 0 and 5 C. After completion of the addition, the mixture was alternately warmed to C. and cooled to 15 C. several times to facilitate the removal of the nitrogen oxide gases. Thereafter the mixture was placed under water pump vacuum pressure for a Nitrogen was then bubbled through the mixture at 50 C. to sweep out the remaining nitrogen oxide gases. Following this the mixture was treated with sodium bicarbonate to assure neutralization of the reaction mixture. The organic and aqueous portions were separated. The organic portion was washed with sodium bicarbonate and then distilled to remove low boiling by-products and to obtain a white solid residue. The latter was fractionally crystallized from carbon tetrachloride to obtain a 3,3,3-trichloro-2-methyl-2-nitropropanol melting at 191 -l92 C. A mixture of the product thus obtained with the product obtained asdescribed in Example 1 gave no depression of the melting point. 1

Example 3 In a manner similar to that described in Example 1, the following 3,3,3trichloro2-alkyl2-nitropropanols are prepared:

3,3,3-trichloro-2-ethyl2-nitropropanol by the reaction of 3,3-dichloro-2-ethylallyl alcohol with dinitrogen tetroxide.

3,3,3-trichloro-2-(normal-propyl) 2 nitropropanol by the reaction of 3,3-dichloro-2-(normal propyl)allyl alcohol with dinitrogen tetroxide.

3,3,3-trichloro-2-( normal butyl 2-nitropropanol by the reaction of 3,3-dichloro-2-(normal butyl)allyl alcohol with dinitrogen tetroxide.

Example 4 In a manner similar to that described in Example 2, the nitroalcohols of Example 3 may be prepared by employing nitric acid in place of dinitrogen tetroxide.

3,3,3trichloro2-methyl-2-nitropropanol is useful in 4 germicidal preparation for the control of bacterial and fungal organisms such as A erobacter aerogenes, Erwinia carotovora, Salmonella typhosa, Staphylococcus aureus, Aspergillas terreus, Penicillium digitatum and Rhizopus nigricans. It is also useful in agricultural applications such as for the control of nematodes, Meloidogyne species.

It is also useful as herbicides, particularly aquatic herbicides for the control of submerged and floating aquatic Weeds. In a representative operation for its use as aquatic herbicide, substantially complete controls of aquatic weeds, Ancharis sp., Cahomba caroliniana, Lysimastrum nummularia and Solvinia rotundifolia were obtained when the weeds were contacted with an aqueous dispersion of 3,3,3trichloro2-methyl-2-nitropropanol at a concentration of 10 parts per million parts of dispersion for a period of 24 hours.

The 3,3-dichloro-2-alkylallyl alcohol employed as starting materials may be prepared by the alkaline hydrolysis of l,l,3-trichloro-2-akyl-lpropene. The preparation may be carried out by heating together in excess water. equimolar proportions of l,l,3-trichloro-2-alkyl-lpropene and sodium hydroxide with stirring until the solution is neutral to litmus. After completion of the heating, the organic and aqueous layers may be separated and the organic layer fractionally distilled to obtain the 3,3-dichloro- Z-alkylallyl alcohol.

- The 1,1,3-trichoro-2-alkyl-lpropene may be prepared by the rearrangement of 1,1,1-trichloro-2-alkyl2-p opene in the presence of a catalyst such as thionyl chloride.

We claim:

1. A method for preparing 3,3,3trichloro-2-alkyl-2- nitropropanol having the formula N02 ClaC-C-CHzOH wherein R is a lower alkyl radical containing from 1 to 4 carbon atoms, inclusive, which comprises intimately mixing together 3,3-dichloro-2-alkylallyl alcohol and a. nitrogen oxide oxidizing agent, said nitrogen oxide oxidizing agent being selected from the group consisting of dinitrogen tetroxide and nitric acid.

2. A method for preparing 3,3,3-trichloro-2-alkyl-2- nitropropanol having the formula N02 ClsC-( 3CH2OH wherein R is a lower alkyl radical containing from 1 to 4 carbon atoms, inclusive, which comprises intimately mixing substantially equimolar proportions of 3,3-di- 'chloro-Z-alkylallyl alcohol and dinitrogen tetroxide in a temperature range of from 50 C. to 30 C.

3. A method for preparing 3,3,3-trichloro-2-alkyl-2- nitropropanol having the formula wherein R'is a lower alkyl radical containing from 1 to 4 carbon atoms, inclusive, which comprises intimately mixing 3,3dichloro-2-alkylallyl alcohol with excess nitric acid in the temperature range of from about 10 C.

--to 30 C.

4. 3,3,3trichloro-2-methyl-2-nitropropanol having the formula 2,844,538 Krug et a1. July 22, 1958 

4. 3,3,3-TRICHLORO-2-METHYL-2-NITROPROPANOL HAVING THE FORMULA 